We investigated the chemical and physical properties of internally functionalized dibenzo[g,p]chrysene (DBC) derivatives. These molecules exhibit chiral double-helicene-like structures that are configurationally stable at ambient temperatures. The internal substituents control the conformational change in the excited state, thereby modulating the emission intensity. Notably, the DBC derivative with a methylenedioxy unit undergoes aromatization through elimination of the internal substituent upon photoexcitation, resulting in the formation of DBC.